Manufacture of thorium oxide and contact masses therefrom



Patented May 28, 1940 UNITED STATES MANUFACTURE OF THORIUM OXIDE AND CONTACT MASSES THEREFROM Richard Miiller and Harry Lee,'Radebeul, near Dresden,

Germany, assignors to Chemische Fabrik von Heyden, A. G., Radebeul, near Dresden, Germany, a corporation of Germany No Drawing. Application October 28, 1937, Se-

rial No. 171,482. In Germany October 29,

7 Claims.

This invention relates to an improved manufacture of thorium oxide and it especially relates to the manufacture of contact masses containing thorium oxide in a highly reactive form from 6 thorium oxalate.

By thermal decomposition of pure thorium oxalate and, as will be shown hereinafter, of complexes containing thorium oxalate to produce thorium oxide there are obtained different oxides 10 according to the conditions:

1. The decomposing temperature above 700 0.: "Dead burnt oxide which cannot be peptised by means of dilute acid and does not dissolveas an ionic dispersion when heated in concentrated hydrochloric or nitric acid (see Kohlschiitter and Frey, Zeitschrift fiir Elektrochemie, vol. 22, page 147).

2. Decomposing temperature below 740-about 500 C.: satisfactorily peptised with dilute acids; does not become soluble oxide capable of ionic dispersion when treated with concentrated hy- 7 drochloric or nitric acid; no luminescence; Rent-- genogram according to Debye and Scherrer: sharp interference lines, also crystal lattice of a 26 high order (Kohlschiitter and Frey, loc. cit. page 3. Decomposing temperature 500-285 C. and lower: As the temperature is lowered the tendency to peptise decreases, but the ionic dispersion 30 solubility increases as luminescence increases. The Rfintgenogram according to Debye and Scherrer gives quite indistinct interference lines only perceptible with difficulty. The crystal latv tice is scarcely formed wherefore the oxide is chemically and physically strongly reactive. The oxide obtained at 285 C. is no longer capable of peptisation; by observing certain conditions with regard to time the oxide is satisfactorily soluble as an ionic dispersion.

If it is desired to obtain the oxides characterised under (3), it is necessary, as more explicitly stated in U. S. Patent No. 2,099,325, to Rudolf Zellmann and Richard Miiller, to consider the duration of the heating-as well as the temperature.

Thus, one must heat at the lowest possible temperature inorder to ensure substantially good decomposition. At a certain period of time the crystal lattice of the thorium oxalate is then destroyed; the crystal lattice of the thorium oxide, however, is either not formed at all or only in incomplete order. At this moment the physical condition of the thorium oxide is especially labile and the oxide, therefore, especially reactive. 56 On heating further the crystal lattice is of better order, the physical condition of the oxide is more stable; the oxide loses its high reactivity.

By raising the temperature both the speed of the decomposition and also the progress of formation in the crystal lattice are increased; the 5 oxide ages. The labile and therefore especially reactive condition of the thorium oxide named above is then more quickly attained but also more quickly passed, so that with'rising temperature it is always more difiicult to interrupt the process 10 of decomposition so as to obtain a highly reactive oxide.

One can, as has been shown in the Zellmann and Miiller patent above referred to, so define the progress of the decomposition reaction and the attainment of the especially labile crystal lattice that the thorium oxide obtained becomes soluble in concentrated hydrochloric acid or nitric acid forming a true salt. which is not coagulated by acids WhereaS thorium oxide prepared ac cording to Mellor Comprehensive Treaties on Inorganic and Theoretical Chemistry, vol. VII, pages 221 and 223, dissolves in water, forming an opalescent sol which is coagulated by acids. An oxide produced by heating for 26 hours at 285 C. 25 dissolves completely in the course of 10-18 minutes boiling in 3-4 times its weight of concentrated nitric acid (specific gravity=1.4) ,to produce thorium nitrate. If the oxalate is heated for too short a time, the dissolution requires a 30 longer period, since the oxalate has not been sufficiently decomposed. By heating to higher temperatures the oxalate is more quickly decomposed. The ageing, however, also rises. At higher temperatures the duration of heating must be shortened as much as possible in order not to render the oxide insoluble owing to ageing.

In the temperature range between 280 and 450 C. the duration of the decomposition can be so adjusted on the foregoing principle that a 40 labile thorium oxide is obtained which is especially reactive. According to the form and pretreatment of the heated thorium oxalate the formation of this highly reactive oxide may be shifted with respect to temperature and time. 45

In the temperature region of about 300 C. the phenomena are particularly distinct and it is easy to produce a highly reactive oxide.

The decomposition of the thorium oxalate differs at these low temperatures also from the 50 reaction at about 450 C. in that at the lower temperature at no period of the decomposition is carbon produced (compare Kohlschiitter and Frey, loc. cit. page 147, Fortschritte auf dem Gebiet der Rontgenstrahlen 37, page 22).

sponding complex salt is obtained. With these thorium oxalate complex salts one can obtain by observing the foregoing mode of operation thoriuznoxide with labile and therefore especially reactive crystal lattice construction. This can be demonstrated also by the solubility in acid.

The following examples illustrate the invention:

EXAMPLE 1 Thorium-ammonium oxalate is heated at 285 C. The interdependence between duration of heating and duration of dissolving is shown in the following table. After the various heating periods samples were heated to boiling with about 4 times their weight of nitric acid (specific gravity=1.4).

Table I Duration Duration of dissolving in about 4 times the weight of heating 7 of HNO; (specific gravity=l.4)

Hours After 2 hours was not dissolved.

After 1 hour was not dissolved.

After 1 hour was not dissolved.

After 24 minutes was partially dissolved. After 22 minutes was partially dissolved. After 18 minutes was completely dissolved. After 16 minutes was completely dissolved.

After 14 minutes was completely dissolved (most labile oxide). After 21- minutes was completely dissolved (beginning of ageing).

. up into contact masses.

' EXAMPLE 2 Thorium oxalate is dissolved in ammonium carbonate solution, the solution is filtered and evaporated and the solid residue is heated at 285 C.

Table II Duration Duration of dissolving in about 4 times the weight of heating of BNO; (specific gravity=l.4)

After 95 minutes was completely dissolved.

After 75 minutes was completely dissolved.

After 60 minutes was completely dissolved.

After 50 minutes was completely dissolved.

After 42 minutes was completely dissolved.

After 36 minutes was labile oxide).

completely dissolved (most "After 50 minutes was completely dissolved (beginning of ageing), 7

. ExAiurLn '3 p Thorium-ammonium oxalate referred toin Example 1 is heated at 400? C.

. Table III r Duration of dissolving in about itimes the weight of neg-ting HNO; (specific gravity-=1. 4)

Hours 4 After 3% hours was fully dissolved.

5 After 2 hours was fully dissolved (labile oxide). 7 Afterd i) hours still not dissolved (already considerably age It will be seenv therefore, that with rising teniperature the time of dissolution is very rapidly prolonged and that the increased speed of the ageing makes it difficult to obtain an especially freely soluble oxide.

When one heats substantially above 400 C.

there occurs in addition to the ageing a separatherefore, in the manufacture of thorium nitrate from monazite sand (see B. R. Btihm, Die Fabrikation der Gliihkiirper fiir Gasgliihlicht, Halle 1910, page 24) to convert the thorium oxalate dissolved in ammonium carbonate for purification directlyinto thorium nitrate. There is thus avoided the unsatisfactory filtration of the highly voluminous or very fine-grained almost colloidal precipitate which is, therefore, collected with diificulty.

The high reactivity of the oxides is exhibited by their specially good efiects when used as catalysts. The oxides obtained may be worked But in order'that the highly active thorium oxide may be distributed in the finest possible state of subdivision on the largest possible surface, it is necessary in order to save the costly thorium oxide, to impregnate intimately known carrier substances like pumice, silica gel, bentonite, fullers earth, clay, xerogels of oxyhydrates or the like with the high reactive oxide.

This is easy when a Zthoriinn'oxalate complex I is used. For making impregnated contact car- I riers for use as catalysts the following procedure may be followed:

ExAnrLr: 4

100 parts by weight of granular pumice having suitably large pores are heated for 1 hours'at 200 C. The pumice is then, while still warm,

- irmnersed in'a saturatedsolutionat 60 C. of ammonium carbonate in which also at 60 C., 80 parts of thorium oxalate has been dissolved. The whole is evaporated to dryness and sifted from powdery constituents if desired. The product is then heated for 24 hours at 315 C. V

. There is obtained a very active contact mass which contains on a'carrier especially reactive thorium oxide in fine state What we claimis: v

1...A ..pro.cess: of manufacturing highly reactive thorium oxide. from thorium oxalate. which consistsirrrheating to a-temperature of about 285 C. to about 450 C. a complex salt containing thorium oxalaterand a compound selected .from the group comprising ammonium carbonate, ammonium oxalate and sodium'carbonate, said heating being for such aperiod of time that a sample taken from the heated mass becomes solublein boiling concentrated nitric acid in the minimum time.

2. Aprocess of manufacturing a catalyst including a carrier and highly reactive thorium oxide, which consists in heating a carrier substance which has been impregnated with a comof subdivision.

} plex salt consisting of thorium oxalate and a monium carbonate, ammonium oxalate and sodium carbonate, said heating being to a temperature of about 285 C. to about 450 C.

3. A process of manufacturing a catalyst including a carrier and highly reactive thorium oxide, which consists in heating a carrier substance which has been impregnated with a complex salt consisting of thorium oxalate and a salt selected from the group consisting of ammonium carbonate, ammonium oxalate and sodium carbonate, said heating being to a temperature of about 285 C. to about 450 C., and for such a period that the solubility of the formed thorium oxide in boiling concentrated nitric acid has reached its culminating point.

4. The process of manufacturing highly reactive thorium oxide,.whieh consists in heating a complex ammonium thorium oxalate to a temperature of about 285 C. for twenty-two to twenty-four hours.

5. Process of manufacturing highly reactive thorium oxide, which consists in heating a complex salt containing thorium oxalate and ammonium carbonate to a temperature of about 285 C. for 25-27 hours.

6. Process of. manufacturing highly reactive thorium oxide, which consists in heating a complex ammonium thorium oxalate to a temperature of about 400 C. for 4- 1 hours.

7. A catalyst including a carrier and highly reactive thorium oxide formed on and distributed over the surface of the carrier by heating a carrier substance which has been impregnated with a complex salt consisting of thorium oxalate and a salt selected from the group consisting of ammonium carbonate, ammonium oxalate and sodium carbonate, said heating'being to a temperature of about 285 C. to about 450" C. for such a period of time that the formed thorium oxide will dissolve in boiling concentrated nitric acid in substantially the minimum time.

RICHARD MULLER. HARRY LEE.

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